EP2230237A1 - Nouveau procédé de fabrication de liaisons d'énaminocarbonyles - Google Patents

Nouveau procédé de fabrication de liaisons d'énaminocarbonyles Download PDF

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Publication number
EP2230237A1
EP2230237A1 EP09155202A EP09155202A EP2230237A1 EP 2230237 A1 EP2230237 A1 EP 2230237A1 EP 09155202 A EP09155202 A EP 09155202A EP 09155202 A EP09155202 A EP 09155202A EP 2230237 A1 EP2230237 A1 EP 2230237A1
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EP
European Patent Office
Prior art keywords
pyrid
chloro
optionally substituted
methyl
compounds
Prior art date
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EP09155202A
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German (de)
English (en)
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Erfindernennung liegt noch nicht vor Die
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Bayer CropScience AG
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Bayer CropScience AG
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Priority to EP09155202A priority Critical patent/EP2230237A1/fr
Priority to ES10715090T priority patent/ES2400148T3/es
Priority to EP10715090A priority patent/EP2408765B1/fr
Priority to JP2012500125A priority patent/JP5543574B2/ja
Priority to US13/256,607 priority patent/US8680285B2/en
Priority to MX2011009734A priority patent/MX2011009734A/es
Priority to DK10715090.6T priority patent/DK2408765T3/da
Priority to PCT/EP2010/001577 priority patent/WO2010105779A1/fr
Priority to CN201080012425.4A priority patent/CN102356077B/zh
Priority to KR1020117024267A priority patent/KR20110128203A/ko
Priority to BRPI1009491A priority patent/BRPI1009491B1/pt
Priority to TW099107401A priority patent/TW201105660A/zh
Publication of EP2230237A1 publication Critical patent/EP2230237A1/fr
Priority to IL215022A priority patent/IL215022A0/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/58—One oxygen atom, e.g. butenolide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/66—Nitrogen atoms

Definitions

  • the present invention relates to a process for the preparation of 4-amino-but-2-enolides.
  • Certain substituted enaminocarbonyl compounds are useful as insecticidal compounds from the EP 0 539 588 A1 known.
  • the international patent applications also describe WO 2007/115644 .
  • WO 2007/115643 and WO 2007/115646 corresponding insecticidal enaminocarbonyl compounds.
  • enaminocarbonyl compounds are synthesized from tetronic acid and an amine according to Scheme 1 below. This procedure is for example in EP 0 539 588 A1 as in Heterocycles Vol. 27, No. 8, pages 1907 to 1923 (1988 ).
  • a disadvantage of this process is, in particular, that anhydrous tetronic acid is required as the starting compound, the production of which is complicated and cost-intensive.
  • tetronic acid is generally prepared starting from acetoacetic ester via a bromination and subsequent hydrogenation (vg1. Synthetic Communication, 11 (5), pages 385 to 390 (1981 )).
  • the total yield of tetronic acid starting from acetoacetic ester is less than 40%, which makes the process less attractive from an industrial point of view.
  • a disadvantage of this process is the low total yield of only 30% and the need to use costly starting materials, such as lithium aluminum hydride (LiAlH 4 ), as reagents.
  • Another method is based on a 4-chloroacetic acid ester, which is reacted with amines ( Heterocycles, Vol. 27, No. 8, 1988, pages 1907 to 1923 ).
  • the reaction to the aminofuran is carried out in one step.
  • the amine is added with glacial acetic acid to a solution of 4-Chloracetessigester in benzene and the resulting mixture is heated for several hours under reflux.
  • the yields of 4-methylamino-2 (5H) -furanone in this synthesis are only 40%.
  • the WO 2007/115644 also describes the preparation of enaminocarbonyl compounds, for example of 4 - [[(6-chloropyridin-3-yl) methyl] (2-fluoroethyl) amino] furan-2 (5H) -one by reacting 4 - [[(2 Fluoroethyl) amino] furan-2 (5H) -one with 2-chloro-5-chloromethylpyridine (see Preparation Examples, Method 3, Example (4)).
  • the reactions are preferably carried out with hydrides of lithium or sodium.
  • enaminocarbonyl compounds are prepared starting from 4- (methoxycarbonyl) -5-oxo-2,5-dihydrofuran-3-ol and an amine.
  • R 1 is hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, halocycloalkyl, alkoxy, alkyloxyalkyl, halocycloalkylalkyl or arylalkyl;
  • Z is hydrogen, alkali metal or alkaline earth metal;
  • A is pyrid-2-yl or pyrid-4-yl or pyrid-3-yl, which is optionally substituted in the 6-position by fluorine, chlorine, bromine, methyl, trifluoromethyl or trifluoromethoxy or pyridazin-3-yl, which optionally substituted in the 6-position by chlorine or methyl or for pyrazine-3-yl or 2-chloro-pyrazine-5-yl or 1,3-thiazol-5-yl, which is optionally substituted in the 2-position Chlorine or methyl
  • enaminocarbonyl compounds which is preferably simple and inexpensive to perform.
  • the enaminocarbonyl compounds obtainable by this desired process should preferably be obtained in high yield and high purity.
  • the intended method should enable the desired target compounds to be obtained without the need for complex purification methods.
  • the process according to the invention is characterized in that compounds of the general formula (II) to give compounds of formula (I), wherein R 1 is hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, halocycloalkyl, alkoxy, alkyloxyalkyl, halocycloalkylalkyl, aryl or arylalkyl; Z is hydrogen, alkali metal or alkaline earth metal; and A is pyrid-2-yl or pyrid-4-yl or pyrid-3-yl which is optionally substituted in the 6-position by fluorine, chlorine, bromine, methyl, trifluoromethyl or trifluoromethoxy or for pyridazin-3-yl, which is optionally substituted in the 6-position by chlorine or methyl or for pyrazine-3-yl or 2-chloro-pyrazine
  • the invention thus provides that the desired enaminocarbonyl compounds of the general formula (I) are prepared by reacting the corresponding compounds of the general formula (II).
  • the desired enaminocarbonyl compounds of the general formula (I) are obtained in good yields in high purity under the preferred reaction conditions according to the invention and specified below, with which the process according to the invention overcomes the abovementioned disadvantages of the processes of the prior art.
  • the desired compounds are obtained in a purity which does not require extensive work-up of the immediate reaction product in general.
  • A is preferably selected from the group consisting of 6-fluoropyrid-3-yl, 6-chloropyrid-3-yl, 6-bromo-pyrid-3-yl, 6-methyl-pyrid-3-yl, 6 Trifluoromethylpyrid-3-yl, 6-trifluoromethoxypyrid-3-yl, 6-chloro-1,4-pyridazin-3-yl, 6-methyl-1,4-pyridazin-3-yl, 2-chloro-1 , 3-thiazol-5-yl or 2-methyl-1,3-thiazol-5-yl, 2-chloro-pyrimidin-5-yl, 2-trifluoromethyl-pyrimidin-5-yl, 5,6-difluoropyrite 3-yl, 5-chloro-6-fluoro-pyrid-3-yl, 5-bromo-6-fluoro-pyrid-3-yl, 5-iodo-6-fluoro-pyrid-3-yl, 5-fluoro -6
  • R 1 is preferably selected from hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, halocycloalkyl, halocycloalkylalkyl and alkoxyalkyl.
  • Z is preferably selected from the group consisting of alkali metals and hydrogen
  • A is more preferably selected from the group consisting of 6-fluoro-pyrid-3-yl, 6-chloro-pyrid-3-yl, 6-bromopyrid-3-yl, 6-chloro-1,4-pyridazine-3 -yl, 2-chloro-1,3-thiazol-5-yl, 2-chloro-pyrimidin-5-yl, 5-fluoro-6-chloro-pyrid-3-yl, 5,6-dichloro-pyrid-3 -yl, 5-bromo-6-chloro-pyrid-3-yl, 5-fluoro-6-bromo-pyrid-3-yl, 5-chloro-6-bromo-pyrid-3-yl, 5,6-dibromo -pyrid-3-yl, 5-methyl-6-chloro-pyrid-3-yl, 5-chloro-6-iodo-pyrid-3-yl and 5-difluoromethyl-6-chloro-
  • R 1 is particularly preferably selected from the group consisting of methyl, ethyl, propyl, vinyl, allyl, propargyl, cyclopropyl, alkoxyalkyl, 2-fluoroethyl, 2,2-difluoro-ethyl and 2-fluoro-cyclopropyl.
  • Z is more preferably selected from the group consisting of hydrogen, sodium and potassium;
  • A is most preferably selected from the group consisting of 6-chloro-pyrid-3-yl, 6-bromo-pyrid-3-yl, 6-chloro-1,4-pyridazin-3-yl, 2-chloro-1 , 3-thiazol-5-yl, 5-fluoro-6-chloro-pyrid-3-yl and 5-fluoro-6-bromo-pyrid-3-yl.
  • R 1 is very particularly preferably selected from the group consisting of methyl, ethyl, n-propyl, n-prop-2-enyl, n-prop-2-ynyl, cyclopropyl, methoxyethyl, 2-fluoroethyl and 2,2-difluoro- ethyl.
  • Z is most preferably selected from the group consisting of sodium and hydrogen
  • starting compounds of the general formula (II) in which the substituents A, Z and R 1 have the preferred meanings mentioned above are used in the process according to the invention.
  • starting compounds of the general formula (II) in which the substituents A, Z and R 1 have the very particularly preferred meanings mentioned above are used in the process according to the invention.
  • alkyl either in isolation or in combination with other terms such as, for example, haloalkyl, alkoxyalkyl, cycloalkylalkyl, halocycloalkylalkyl and arylalkyl, is understood in the context of the present invention to mean a radical of a saturated, aliphatic hydrocarbon group having 1 to 12 carbon atoms, which can be branched or unbranched.
  • C 1 -C 12 -alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, hexyl, n -heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • C 1 -C 6 -alkyl radicals are particularly preferred.
  • Particularly preferred are C 1 -C 4 -alkyl radicals, especially methyl and ethyl.
  • alkenyl is a linear or branched C 1 -C 12 alkenyl radical which has at least one double bond, for example vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 , 3-butadienyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,3-pentadienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, and 1,4 -Hexadienyl, understood.
  • Preferred are C 2 -C 6 -alkenyl radicals and particularly preferred are C 2 -C 4 -alkenyl radicals.
  • alkynyl is understood according to the invention as meaning a linear or branched C 3 -C 12 -alkynyl radical which has at least one triple bond, for example ethynyl, 1-propynyl and propargyl. Preferred of these are C 3 -C 6 -alkynyl radicals and particularly preferred are C 3 -C 4 -alkynyl radicals.
  • the alkynyl radical can also have at least one double bond.
  • cycloalkl is understood according to the invention as meaning a C 3 -C 8 -cycloalkyl radical, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Preferred of these are C 3 -C 6 -cycloalkyl radicals.
  • aryl is understood according to the invention to mean an aromatic radical having 6 to 14 carbon atoms, preferably phenyl.
  • arylalkyl is understood to mean a combination of radicals "aryl” and “alkyl” defined according to the invention, the radical generally being bound via the alkyl group, examples of which are benzyl, phenylethyl or .alpha.-methylbenzyl, benzyl being particularly preferred.
  • halogen-substituted radicals for example haloalkyl
  • radicals which are mono- or polysubstituted to the maximum possible number of substituents For multiple halogenation, the halogen atoms may be the same or different.
  • Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
  • alkoxy either alone or in combination with other terms, such as, for example, haloalkoxy, is understood herein to mean a radical O-alkyl, the term “alkyl” having the meaning given above.
  • Optionally substituted radicals may be monosubstituted or polysubstituted, wherein in a multiple substitution the substituents may be the same or different.
  • Another object of the present invention are compounds of the formula (II) in which the radicals A, Z and R 1 are as defined above.
  • radicals A, Z and R 1 are as defined above and R 2 is alkyl, aryl or arylalkyl.
  • the compound (II) may also be in an isomeric form.
  • the 2,4-dioxotetrahydrofuran-3-carboxylates of the general formula (IV) used as starting materials can be prepared by processes known from the prior art ( R. Anster, Ber., 1912, 45, 2374 ; E. Benary, Ber., 1912, 45, 3682 ).
  • the amines of the general formula (III) are commercially available or can be prepared by methods known from the literature (cf., for example, S. Patai "The Chemistry of Amino Group", Interscience Publishers, New York, 1968).
  • reaction according to the invention of the compounds of the general formula (II) shown above to give compounds of the general formula (I) is carried out in the presence of solvents (diluents).
  • solvents are advantageously used in such an amount that the reaction mixture remains easy to stir throughout the process.
  • Suitable solvents for carrying out the process according to the invention are all organic solvents which are inert under the reaction conditions.
  • halogenated hydrocarbons especially chlorinated hydrocarbons, such as tetrachlorethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; Ethers, such as ethyl propyl ether, methyl tert-butyl ether, n -butyl ether, anisole, phenetole, cyclohexylmethyl ether, dimethyl ether, diethyl ether, dimethyl glycol, diphenyl ether, dipropyl ether, diisopropyl ether, di- n
  • the reaction according to the invention is preferably carried out in a solvent which is selected from the group consisting of dioxane, butyronitrile, propionitrile, acetonitrile, DME, toluene, methyl THF, dichlorobenzene, chlorobenzene, n-heptane, isobutanol, n-butanol , Ethanol, methyl tert-butyl ether, isopropyl ethyl ether and mixtures thereof.
  • a solvent which is selected from the group consisting of dioxane, butyronitrile, propionitrile, acetonitrile, DME, toluene, methyl THF, dichlorobenzene, chlorobenzene, n-heptane, isobutanol, n-butanol , Ethanol, methyl tert-butyl ether, isopropyl ethyl ether and mixtures
  • the reaction can also be carried out in the presence of water.
  • reaction of the compounds of the general formula (II) is preferably carried out in the presence of a Br ⁇ nsted acid.
  • inorganic acids for example phosphoric acid (H 3 PO 4 ), sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), hydrobromic acid (HBr), hydrofluoric acid (HF) or potassium hydrogen sulfate (KHSO 4 ), are used.
  • the individual acids can be used both in anhydrous form and in water-containing form, for example as 85% phosphoric acid or 37% hydrochloric acid, ie in particular in forms in which the acids are commercially available.
  • suitable organic acids are trifluoroacetic acid, acetic acid, methanesulfonic acid and p-toluenesulfonic acid.
  • phosphoric acid, sulfuric acid, potassium hydrogensulfate and trifluoroacetic acid are particularly preferred.
  • the reaction for the preparation of the compounds of the general formula (I) can generally be carried out in vacuo, at atmospheric pressure or under excess pressure.
  • the temperatures used can also vary depending on the substrates used and are easily determined by those skilled in the art through routine experimentation.
  • the reaction for producing the compounds of the general formula (I) may be carried out at a temperature of 20 to 200 ° C, preferably 20 to 150 ° C.
  • the water of reaction may be removed by distillation of a portion of the solvent as an azeotrope. With high-boiling solvents, this can be done in a vacuum. This process generally achieves a quantitative turnover.
  • the solvent may be removed by distillation after the end of the reaction. This can be done under normal pressure or reduced pressure at room temperature or elevated temperatures.
  • the isolation of the desired compounds of the general formula (I) can also be carried out, for example, by crystallization.
EP09155202A 2009-03-16 2009-03-16 Nouveau procédé de fabrication de liaisons d'énaminocarbonyles Ceased EP2230237A1 (fr)

Priority Applications (13)

Application Number Priority Date Filing Date Title
EP09155202A EP2230237A1 (fr) 2009-03-16 2009-03-16 Nouveau procédé de fabrication de liaisons d'énaminocarbonyles
PCT/EP2010/001577 WO2010105779A1 (fr) 2009-03-16 2010-03-12 Nouveau procédé de préparation de composés énaminocarbonylés
CN201080012425.4A CN102356077B (zh) 2009-03-16 2010-03-12 制备烯胺羰基化合物的新方法
JP2012500125A JP5543574B2 (ja) 2009-03-16 2010-03-12 エナミノカルボニル化合物の新規製造方法
US13/256,607 US8680285B2 (en) 2009-03-16 2010-03-12 Method for producing enaminocarbonyl compounds
MX2011009734A MX2011009734A (es) 2009-03-16 2010-03-12 Nuevo procedimiento de preparacion de compuestos de enaminocarbonilio.
DK10715090.6T DK2408765T3 (da) 2009-03-16 2010-03-12 Ny fremgangsmåde til fremstilling af enaminocarbonyl-forbindelser
ES10715090T ES2400148T3 (es) 2009-03-16 2010-03-12 Nuevo procedimiento de preparación de compuestos de enaminocarbonilo
EP10715090A EP2408765B1 (fr) 2009-03-16 2010-03-12 Nouveau procédé de préparation de composés énaminocarbonylés
KR1020117024267A KR20110128203A (ko) 2009-03-16 2010-03-12 엔아미노카보닐 화합물의 신규 제조방법
BRPI1009491A BRPI1009491B1 (pt) 2009-03-16 2010-03-12 processo para produção de enaminocarbonilas, e seus intermediários
TW099107401A TW201105660A (en) 2009-03-16 2010-03-15 Novel process for the preparation of enaminocarbonyl compounds
IL215022A IL215022A0 (en) 2009-03-16 2011-09-07 Novel process for the preparation of enaminocarbonyl compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09155202A EP2230237A1 (fr) 2009-03-16 2009-03-16 Nouveau procédé de fabrication de liaisons d'énaminocarbonyles

Publications (1)

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EP2230237A1 true EP2230237A1 (fr) 2010-09-22

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EP09155202A Ceased EP2230237A1 (fr) 2009-03-16 2009-03-16 Nouveau procédé de fabrication de liaisons d'énaminocarbonyles
EP10715090A Active EP2408765B1 (fr) 2009-03-16 2010-03-12 Nouveau procédé de préparation de composés énaminocarbonylés

Family Applications After (1)

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EP10715090A Active EP2408765B1 (fr) 2009-03-16 2010-03-12 Nouveau procédé de préparation de composés énaminocarbonylés

Country Status (12)

Country Link
US (1) US8680285B2 (fr)
EP (2) EP2230237A1 (fr)
JP (1) JP5543574B2 (fr)
KR (1) KR20110128203A (fr)
CN (1) CN102356077B (fr)
BR (1) BRPI1009491B1 (fr)
DK (1) DK2408765T3 (fr)
ES (1) ES2400148T3 (fr)
IL (1) IL215022A0 (fr)
MX (1) MX2011009734A (fr)
TW (1) TW201105660A (fr)
WO (1) WO2010105779A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP3150754A1 (fr) 2015-09-29 2017-04-05 Staubli Lyon Système de contrôle d'une mécanique jacquard, mécanique jacquard et métier à tisser équipés d'un tel système

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011051151A1 (fr) * 2009-10-26 2011-05-05 Bayer Cropscience Ag Nouvelle forme solide de 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one

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CH503722A (de) 1969-05-28 1971-02-28 Lonza Ag Verfahren zur Herstellung von Tetronsäure
EP0123095A2 (fr) 1983-03-25 1984-10-31 Bayer Ag 1,4-Dihydropyridine lactones, chromone- ou thiochromone-substitués, leurs procédés de préparation et leur application comme médicaments
EP0153615A1 (fr) 1984-02-09 1985-09-04 Lonza Ag Procédé pour la préparation d'acide tétronique
EP0539588A1 (fr) 1990-07-05 1993-05-05 Nippon Soda Co., Ltd. Derive d'amine
WO1993022305A1 (fr) * 1992-04-28 1993-11-11 American Home Products Corporation Derives d'acides tetronique, thiotetronique et tetramique en tant qu'inhibiteurs de la phospholipase a¿2?
US5905090A (en) * 1998-04-29 1999-05-18 Italfarmaco S.P.A. Analogues of the active metabolite of leflunomide
WO1999038846A1 (fr) * 1998-01-30 1999-08-05 Procept, Inc. Agents immunosuppresseurs
WO2007115646A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués utilisés comme insecticides
WO2007115644A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
WO2007115643A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
EP2042496A1 (fr) 2007-09-18 2009-04-01 Bayer CropScience AG Procédé de fabrication de 4-aminobut-2-énoïque

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CH503722A (de) 1969-05-28 1971-02-28 Lonza Ag Verfahren zur Herstellung von Tetronsäure
EP0123095A2 (fr) 1983-03-25 1984-10-31 Bayer Ag 1,4-Dihydropyridine lactones, chromone- ou thiochromone-substitués, leurs procédés de préparation et leur application comme médicaments
EP0153615A1 (fr) 1984-02-09 1985-09-04 Lonza Ag Procédé pour la préparation d'acide tétronique
EP0539588A1 (fr) 1990-07-05 1993-05-05 Nippon Soda Co., Ltd. Derive d'amine
WO1993022305A1 (fr) * 1992-04-28 1993-11-11 American Home Products Corporation Derives d'acides tetronique, thiotetronique et tetramique en tant qu'inhibiteurs de la phospholipase a¿2?
WO1999038846A1 (fr) * 1998-01-30 1999-08-05 Procept, Inc. Agents immunosuppresseurs
US5905090A (en) * 1998-04-29 1999-05-18 Italfarmaco S.P.A. Analogues of the active metabolite of leflunomide
WO2007115646A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués utilisés comme insecticides
WO2007115644A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
WO2007115643A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
EP2042496A1 (fr) 2007-09-18 2009-04-01 Bayer CropScience AG Procédé de fabrication de 4-aminobut-2-énoïque

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GIORGIO BERTOLINI, MARIO AQUINO, MAURO BIFFI, GAETANO D'ATRI ET AL.: "A new rational hypothesis for the pharmacophore of the active metabolite of leflunomide, a potent immunosuppressive drug", J. MED. CHEM., vol. 40, 1997, pages 2011 - 2016, XP002548068 *
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EP3150754A1 (fr) 2015-09-29 2017-04-05 Staubli Lyon Système de contrôle d'une mécanique jacquard, mécanique jacquard et métier à tisser équipés d'un tel système

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BRPI1009491A2 (pt) 2015-08-18
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MX2011009734A (es) 2011-09-29
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JP2012520335A (ja) 2012-09-06
US8680285B2 (en) 2014-03-25
EP2408765B1 (fr) 2013-01-23
CN102356077B (zh) 2014-07-23
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